Polymerizable imidazolidinones

ABSTRACT

Novel polymerizable imidazolidinone monomers, useful in the preparation of self-crosslinking polymers, have the general structure ##STR1## wherein R 1  is H or a C 1  -C 6  linear or branched alkyl or hydroxyalkyl group; X is a divalent radical selected from the group consisting of ##STR2## with R being H or CH 3 , m being 0-5, and n being 1-5; R 2  is H or CH 3  ; R 3  is H or ##STR3## with R&#39; as defined above; and R 4  and R 5  are independently H or linear or branched C 1  -C 4  alkyl groups. In a preferred embodiment, aqueous emulsions of the imidazolidinone-containing polymers (e.g. 45-60% vinyl acetate, 34-52% butyl acrylate, and 3-6% imidazolidinone) and an acid-curing catalyst (e.g. ZnCl 2 ) are used as formaldehyde-free binders for nonwoven textiles.

This application is a continuation of application Ser. No. 473,922,filed Mar. 10, 1983, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to novel polymerizable imidazolidinone monomers,their preparation, and their use to form self-crosslinking polymerswhich are thermosettable without the release of formaldehyde. It alsorelates to the use of such polymers in emulsion form as nonwovenbinders.

It is well-known in the art to employ self-crosslinking polymers, eitherin emulsion or solution form, as coatings, binders, or adhesives for avariety of substrates. Self-crosslinking polymers are distinguished fromcrosslinkable polymers in that the latter contain a functionality, suchas a carboxyl group, which can only be crosslinked by the addition of aco-reactant (i.e., crosslinker) to the polymer emulsion or solution. Atypical crosslinkable system can be represented as follows: ##STR4##

In contrast, self-crosslinking polymers contain a functionality which isself-reactive and consequently do not require the use of a coreactantspecies per se. A typical self-crosslinking system can be represented asfollows: ##STR5##

The advantages of the self-crosslinking polymer systems are theirsimplicity, economy, and particularly their efficiency. Such systemshave been used as textile adhesives, non-woven binders, pigment bindersfor glass fabrics, and fabric finishing agents for hand and weightmodification. On curing, such systems produce textile products withexcellent durability to washing and dry cleaning. They have also beenused in pigment printing and dyeing and as a binder for paper.

Both the self-crosslinking and crosslinkable polymer systems of theprior art suffer from the disadvantage that toxic free formaldehyde ispresent either during the curing or the preparation of the polymers. Theself-crosslinking systems, which are typically formaldehyde-amidepolymeric adducts containing methylolacrylamide repeating units,liberate formaldehyde during curing of the crosslinked thermosetpolymer. The crosslinkable systems, which are typically based onurea-formaldehyde or melamine-formaldehyde resins and crosslinkers, maycontain residual free formaldehyde.

In addition to the odor problems created by the presence of freeformaldehyde, the dermatitic effect is a serious problem. The exposureof operating personnel and cosumers to formaldehyde has been a recentconcern of both industry and regulatory agencies. This has lead to thesearch for formaldehyde-free systems, especially self-crosslinking,formaldehyde-free systems for use as nonwoven binders.

SUMMARY OF THE INVENTION

The present invention provides, as a composition of matter, animidazolidinone of the general structure: ##STR6## wherein R¹ ishydrogen or a C₁ -C₆ linear or branched alkyl group when attached to anitrogen; X is a divalent radical selected from the group consisting of##STR7## with R being a hydrogen or a methyl group, with m being aninteger from 0 to 5, and with n being an integer from 1 to 5, preferablym or n being 1; R² is hydrogen or a methyl group; R³ is hydrogen or a##STR8## group with R¹ being hydrogen or a linear or branched C₁ -C₆alkyl or hydroxyalkyl when attached to an oxygen; and R⁴ and R⁵ areindependently hydrogen or a linear or branched C₁ -C₄ alkyl group.

It also provides homopolymers and polymers thereof with monomer(s)containing at least one ethylenically unsaturated group.

In a preferred embodiment it provides emulsion (latex) polymerscontaining about 1-15%, preferably 3-6%, by weight of the above monomersand about 85-99%, preferably 94-97%, of an ethylenically unsaturatedmonomer, such as ethylene, vinyl acetate, ethyl acrylate, butylacrylate, methyl methacrylate and the like, for use as formaldehyde-freebinders for nonwoven textiles. A typical polymer contains about 45-60%vinyl acetate, 34-52% butyl acrylate, and about 3-6% of theself-crosslinking imidazolidinone.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The novel monomers herein are typically prepared by reacting anethylenically unsaturated urea derivative with glyoxal. The ureaderivatives are usually well known compounds previously reported in thechemical literature. Methods for their preparation are described inSynthetic Organic Chemistry by R. B. Wagner and H. D. Zook, John Wiley &Sons, 1963, p. 645. Two suitable methods include the reaction ofisocyanates with amines, ##STR9## wherein R or R' may be an unsaturatedgroup, and the reaction of amines with urea, i.e. ##STR10## wherein R"is an unsaturated group.

In the typical isocyanate reaction, the isocyanate compound is dissolvedin an aprotic dry solvent such as toluene at about 40% concentration.The entire reaction system is protected from moisture by suitable dryingtubes, inert gas purge, or the like. The amine is slowly added to thesolution at a temperature not exceeding 10°-15° C. In the case ofammonia or simple alkyl amines, this component is a gas and it isbubbled subsurface. The reaction is exothermic and adequate cooling maybe required. The urea derivative usually precipitates as it forms andmay be recovered from the reaction mixture by filtration. The derivativeis then washed and dried.

In the typical amine reaction, the amine and urea are combined andheated at 120°-150° C. with the evolution of ammonia. When the reactionmixture reaches the required weight, the heating is stopped and thesolid mass is recrystallized to recover the urea derivative.

In the imidazolidinone preparation, the urea compound is dissolved insufficient water and gloxal to provide a solution of about 50%theoretical solids (based on imidazolidinone being prepared). Theglyoxal reagent, used in stoichiometric amounts, may vary in form (e.g.40% aqueous solution, 80% powder, p-dioxane diol, or the like). The pHof the mixture is adjusted to 7-7.5 with sodium hydroxide. Heat isapplied to raise the temperature of the mixture to 45°-80° C. to effectcomplete reaction. The reaction is monitored by titrating for glyoxalcontent. When the reaction is complete, the monomer solution isgenerally diluted to 40% solids by the addition of water and the dilutedmixture treated with activated charcoal. When the hydroxyl groups of theimidazolidinone ring are substituted with alkyl groups, suitablestarting materials for the imidozolidinones may be prepared usingwell-known methods described in Synthesis 243 (1973a).

The above imidazolidinone monomers are useful as vinyl polymerizablemonomers (i.e. monomers polymerizable by vinyl type polymerizationprocedures). They may be used to form homopolymers or their mixtures maybe used to form polymers thereof. They may also be used to form additionpolymers with other ethylenically unsaturated monomers. The polymers maybe prepared by solution, emulsion, precipitation, suspension, or bulkpolymerization techniques. The preferred method is emulsionpolymerization.

Suitable comonomers include one or more monomers containing at least oneethylenically unsaturated group such as (meth)acrylonitrile;(meth)acrylic acid and the esters, amides and salts thereof; itaconicacid and its functional derivatives, preferably the esters; maleicanhydride; maleic and fumaric acids and the esters thereof; vinyl ethersand esters; styrene; ethylene; vinyl and vinylidene chlorides; and thelike.

The preferred addition polymers for use as formaldehyde-free binders fornon-woven textiles are polymers containing about 1-15%, preferably 3-5%,by weight of the above imidazolidinone monomers and about 99-85%,preferably 97-95%, by weight of one or more ethylenically unsaturatedmonomers such as ethylene, vinyl acetate, ethyl acrylate, butylacrylate, or methyl methacrylate. The preferred imidazolidinone monomersfor this use include3-(methacryloxyethyl)-4,5-dihydroxy-2-imidazolidinone,1-ethyl-3-allyl-4,5-dihydroxy-2-imidazolidinone, and3-allyl-4,5-dihydroxy-2-imidazolidinone.

The following examples will more fully illustrate the embodiments ofthis invention. In the examples, all parts and percentages are given byweight and all temperatures are in degrees Celsius unless otherwisenoted.

EXAMPLE I

This example describes the preparation of the3-(methacryloxyethyl)-4,5dihydroxy-2-imidazolidinone (MEDHEU). Thetwo-step reaction sequence was as follows: ##STR11##

A three liter round bottom flask equipped with a thermometer, agitator,condenser, drying tube and a gas inlet tube was charged with 1500 ml. of3 A° sieve dried toluene and 340 g. (2.195 moles) of β-isocyanatoethylmethacrylate. With agitation, the mixture was cooled to 5° C. in an icebath. While maintaining the reaction temperature at 5°-10° C., 39.6 g.ammonia gas was bubbled subsurface over a period of 7 hrs. After theaddition was completed, the temperature of the reaction mixture wasallowed to rise to 25° C. The precipitated urea product was recovered byfiltration, washed with fresh toluene, and dried in a vacuum dessicatorto constant weight. Yield was 369 g. (98%). IR analysis (1715 cm⁻¹, 1685cm⁻¹, 1600 cm⁻¹) and nitrogen analysis (16.3%) were consistent withmono-substituted urea structure of N-methacryloxyethyl urea.

A one-liter four neck flask equipped with an agitator, thermometer,condenser and pH electrode/meter was charged sequentially with 13 g.distilled water, 95.6 g of 43.6% aqueous glyoxal solution, 0.25 g.monomethyl ether of hydroquinone, and 125 g. of the above urea. Themixture was agitated until complete solution was achieved. The pH of themixture was adjusted to 7.0-7.5 with 6.25N NaOH (25% W/V) and themixture was heated at 60° C. for 5 hr. At the end of this period,analysis for glyoxal indicated 95% reaction. The mixture was dilutedwith 597 g. distilled water, purified by slurrying with 8.3 g. of a highsurface area activated charcoal, and filtered through diatomaceousearth. The active solids content was 20% MEDHEU.

EXAMPLE II

This example describes the preparation of1-ethyl-3-allyl-4,5-dihydroxy-2-imidazolidinone (EADHEU). The two-stepreaction sequence was as follows: ##STR12##

A two-liter reactor equipped with an agitator, thermometer, condenserwith drying tube and equalized dropping funnels was charged with 800 ml.of sieve dried toluene and 80 g. allyl amine. With agitation, themixture was cooled to 10° C. and 100 g. of ethylisocyanate was addedover a 2 hr. period. The reaction was exothermic and the temperature wasmaintained at 10°-15° C. throughout the addition by external cooling.After the addition was completed, the toluene was vacuum distilled fromthe mixture at 40° C./20 mm. Hg. The viscous liquid was titurated withheptane to precipitate the N-ethyl, N'-allyl-urea. The nitrogen contentwas 21.3% (21.5% theoretical).

A 500 ml. flask equipped with a thermometer, condenser, and agitator wascharged with 75 g. of the above urea, 91.1 g. of 43% aqueous glyoxal,and 87.5 g. distilled water. After complete dissolution of thereactants, the pH was adjusted to 7.0-7.5 with 25% sodium hydroxide andthe mixture heated at 80°-85° C. for 4.5 hr. The glyoxal content wasmonitored during the reaction period. At the end of the heating period,no glyoxal was detected, indicating 100% reaction. The mixture wasdiluted with water and purified as before. The active solid content was26.5% EADHEU.

Carbon-13 NMR analysis of the aqueous solution confirmed the presence ofthe imidazolidinone ring structure. The chemical shifts were as follows:

    ______________________________________                                        Oc ppm      Pattern     Assignment                                            ______________________________________                                        12.9        Quartet                                                                                    ##STR13##                                            35.3        Triplet                                                                                    ##STR14##                                            42.5        Triplet                                                                                    ##STR15##                                            84.3        Doublet                                                                                    ##STR16##                                            117.0       Triplet                                                                                    ##STR17##                                            132.8       Doublet                                                                                    ##STR18##                                            158.8       Singlet      .sub.--CO                                            ______________________________________                                    

EXAMPLE III

This example illustrates the preparation of additional imidazolidinonemonomers using the procedure of Example II.

Part A

3-Allyl-4,5-dihydroxy-b 2-imidazolidinone (ADHEU) was prepared using93.5 g. N-allyl urea, 109 g. 43% aqueous glyoxal, and 60 g. distilledwater. The reaction was carried out for 6 hr. at 45°-50° C. Yield was87%. The reactive solid content was 43.6%. The monomer had the followingstructure: ##STR19##

Part B

1-Methyl-3-(methacryloxyethyl)-4,5-dihydroxy-2-imidazolidinone wasprepared using 37.2 g. N-methyl-N'-methacryloxyethyl urea, 25.7 g. 43%aqueous glyoxal, and 6 g. water. The reaction was carried out for 6.5hr. at 60° C. Yield was 94%. The mixture was diluted with 124 g.distilled water. The active solids content was 25%. The monomer had thefollowing structure: ##STR20##

Part C

1-Butyl-3-(2-methyl-1-propenyl)-4,5-dihydroxy-2-imidazolidinone wasprepared using 85 g. N-butyl-N'-(2-methyl-1-propenyl)urea, 36.3 g. 80%aqueous glyoxal, and 106 g. water. The reaction was carried out for 8hr. at 80° C. Yield was 100%. The mixture was diluted with 58 g.distilled water. The active solids content was 39.5%. The monomer hadthe following structure: ##STR21##

EXAMPLE IV

This example describes the preparation of3-(β-hydroxyethyl-2-maleoxyethyl)-4,5-dihydroxy-2-imidazolidinone(EMDHEU). The three-step reaction sequence was as follows: ##STR22##

A two-liter round bottom flask, fitted with an agitator, thermometer,condenser, and drying tube, was charged with 1000 ml. of sieve driedtoluene, 208 g. (2.0 moles) of β-hydroxyethyl urea and 196 g. (2.0moles) of maleic anhydride. The reaction mixture was heated to 85°-90°C. Initially the mixture formed two distinct immiscible liquid phases.As the reaction proceeded, the mixture became homogeneous. Heating wascontinued until infrared analysis showed complete disappearance of theanhydride bands and the acid number of the reaction mixture indicatedcomplete reaction (280 mg. KOH/gm. sample actual vs. 277 theory). Thetoluene was removed by vacuum stripping. A total of 393.5 g. of (97.5%yield) of N-(2-maleoxyethyl)urea was obtained.

While maintaining the above reaction mixture at 80°-85° C., 0.9 g. Na₂CO₃ was added and the subsurface addition of ethylene oxide (115 g.) wascarried out over 6 hours. At the end of the ethylene oxide addition, theacid number was 28 corresponding to a reaction efficiency of 91%. Theresidual ethylene oxide was removed by a brief vacuum stripping at 80°C. A total of 464 g. of N-(β-hydroxyethyl-2-maleoxyethyl)urea having anacid number of 15 (corresponding to 95% reaction) was obtained.

The above reaction mixture was cooled to 30° C. and 100 g. distilledwater and 254 g. of 43% aqueous glyoxal were added. It was adjusted topH 7.0-7.5 with 25% W/V sodium hydroxide and heated at 60° C. for 2 hr.After this time, no glyoxal was detected in the reaction mixture. It wasdiluted to 20% solids with 1917 g. water, treated with charcoal andfiltered. Yield was 100%.

EXAMPLE V

This example describes the preparation of3-(methacryloxy-2-hydroxypropoxyethyl)-4,5-dihydroxy-2-imidazolidinone(MPEDHEU). The two-step reaction sequence was as follows: ##STR23##

A 500 ml. round bottom reaction flask fitted with a thermometer,condenser and agitator was charged with 142 g. (1 mole) of glycidylmethacrylate, 0.25 g. monomethyl ether of hydroquinone, 0.75 g.tetramethyl ammonium chloride and 104 g. β-hydroxyethyl urea (1.0 mole).The mixture was heated and stirred at 80°-85° C. until gas-liquidchromatographic (GLC) analysis indicated complete consumption of theglycidyl methacrylate (about 6 hrs.). This is always indicated bytesting the water solubility of the reaction mixture. The product iswater soluble and near completion of the reaction no turbidity isobserved in test samples. The reaction mixture was then cooled to 30° C.and 132 g. of water were added.

A portion of the above reaction mixture containing 154 g. ofN(methacryloxy-2-hydroxypropoxyethyl)urea (0.407 moles) was charged to a250 ml. reaction vessel equipped with a stirrer, thermometer, andcondenser. To this was added 27.7 g. of glyoxal trimer (0.397 mole83%active) and 7.5 g. distilled water. The pH of the mixture was adjustedto 7.0-7.5 with 25% W/V NaOH and the mixture was heated at 65° C. for 3hr. The glyoxal content was 0% indicating 100% reaction. The reactionmixture was treated with 4 gms. of activated carbon and filtered. Theactive solids content was 40%.

EXAMPLE VI

This example describes the preparation of3-(1-propenoxy-2-hydroxypropoxyethyl)-4,5-dihydroxy-2-imidazolidinone.

The reaction was carried out in a similar manner to that of Example Vexcept that 114 g. allylglycidyl ether (1 mole) was used in place of theglycidyl methacrylate and 135 g. (1 mole) of 43% aqueous glyoxal wasused instead of the 83% aqueous glyoxal trimer. The active solidscontent was 45%. The monomer had the following structure: ##STR24##

EXAMPLE VII

This example describes the preparation of3-allyl-4,5-dimethoxy-2-imidazolidinone.

A mixture of 100 g. of N-allyl urea (1 mole), 69.9 g. of 83% glyoxal (1mole), and 750 g. methanol is stirred for 1 hr. at 35°-40° C. A total of50 g. of a cation exchange resin (sulfonated polystyrene, H⁺ form, 5.2meq./dry g.) is then added. The mixture is stirred for 1 hr. at reflux(about 70° C.). The catalyst is removed by filtration, and the reactionmixture is concentrated by vacuum distillation of the solvent. Theresulting product should be 232 g. of a syrup at 80% active solids(based on 100% yield). The monomer will have the following structure:##STR25##

EXAMPLE VIII

This example describes the preparation of1-ethyl-3-vinyl-4,5-dihydroxy-2-imidazolidinone.

A total of 172 g. of N-vinyl-N'-ethyl urea (1 mole), prepared asdescribed in J. Poly. Science, Part A-1, Vol. 7, 35-46 (1969), isdissolved with stirring in 200 g. distilled water. To this solution isadded 69.9 g. 83% glyoxal (1 mole). The pH of the mixture is adjusted to7.5 with 0.5N NaOH, and the mixture is heated at 70° C. for 4.5 hr. oruntil a determination of the glyoxal content indicates completeconversion. The mixture is diluted with 133 g. distilled water and 0.23g. monomethyl ether of hydroquinone. The diluted mixture is treated with2 g. activated charcoal and filtered. The final product should beaqueous solution of the monomer at 80% solids (based on 100% yield). Themonomer will have the following structure: ##STR26##

EXAMPLE IX

This example describes the preparation of a surfactant-stabilized latexpolymer containing 58.9% vinyl acetate, and 35.3% butyl acrylate, 5.8%of the MEDHEU monomer of Example I. It also describes its evaluationafter crosslinking and its use as a binder for non-woven textiles.

Part A

A two-liter four neck flask was fitted with a thermometer, condenser,agitator, subsurface nitrogen purge, and suitable addition funnels. Tothe flask was added:

400 g. distilled water

2.0 g. 20% sodium dodecyl benzene sulfonate

2.5 g. 70% ethoxylated nonyl phenol (30 moles EO)

0.5 g. sodium acetate

0.8 g. sodium persulfate

The mixture was purged subsurface with nitrogen at a rapid rate for 15min. The gas rate was then reduced, and 50 g. vinyl acetate and 5 g.butyl acrylate were added. Agitation was started.

A monomer pre-emulsion was prepared by combining the followingingredients in a beaker and subjecting the mixture to high speed mixing:125 g. of the MEDHEU monomer at 20%; 10 g. of 30 mole ethoxylated nonylphenol at 70%; 12 g. of 20% sodium dodecyl benzene sulfonate; 200 g.vinyl acetate; 145 g. butyl acrylate. The mixture was transferred to aone-liter dropping funnel. A catalyst solution, designated S-2, wasprepared by dissolving 0.7 g. sodium persulfate in 30 g. distilledwater.

The initial reactor charge was heated to 72°-75° C. The mixture began toreflux at 72° C. Polymerization was indicated by a change in themixture's appearance. After the refluxing stopped, the monomerpre-emulsion (S-1) and the catalyst solution (S-2) were slowly added tothe reactor over a 4 hr. period at 72°-75° C. After the addition wascomplete, the batch was held for 1 hr. at 75° C., cooled, anddischarged.

The resulting latex had a solids content of 48%. Yield was 98%. Theproperties of the latex were as follows: a pH of 4.1; intrinisicviscosity of 0.90 dl./g. in dimethyl formamide (DMF); Brookfieldviscosity of 175 cps.; particle size of 0.17 nm.; and unfiltered grit(200 mesh) of 40 ppm. No formaldehyde was detected (the detectable limitwas 5 ppm).

Part B

In order to evaluate the self-crosslinking capabilities and formaldehydecontent of the above latex polymer, films were drawn on polyethylene asuncatalyzed or catalyzed (0.5% oxalic acid on polymer solids) latices.The films were air dried overnight or cured by heating in a forced airdraft oven at 130° C. for 5 min. The film specimens were then weighedinto enough DMF to make a 1% solution and refluxed for 2 hours. Thecooled mixture was filtered, and the amount of soluble polymer wasdetermined by oven solids. A determination of % insolubles was thenmade. A comparison polymer containing 3% N-methylolacrylamide (NMA), aknown self-crosslinking monomer, was also evaluated.

    ______________________________________                                                                 Invention Latex                                                   Comparison Latex                                                                          (containing                                                       (containing NMA)                                                                          MEDHEU)                                              ______________________________________                                        Formaldehyde on latex                                                                        3400 ppm      None                                             Insolubles - air dried                                                                       38%           45%                                              Insolubles - catalyzed and                                                                   64%           70%                                              air dried                                                                     Insolubles - catalyzed and                                                                   89%           90%                                              oven cured                                                                    ______________________________________                                    

The results show the latex containing the self-crosslinkingimidazolidinone-containing polymer of the present invention contained noformaldehyde and that it crosslinked as efficiently as the comparisonlatex containing the self-crosslinking polymer of the prior art.

Part C

The above latex polymers were evaluated as binders for non-woventextiles.

A substrate web of 100% polyester fiber was prepared by carding andsubsequently lightly thermally bonded. The latex containing the MEDHEUpolymer was formulated with 1% (dry basis) zinc chloride catalyst. Thecomparison latex containing the NMA polymer was formulated with 0.5%oxalic acid. The binders were diluted with water to 15% solids. The webwas passed through a bath saturated with the binder formulation andsqueezed through nip rolls to remove excess binder. Binder add-on wascontrolled to 40%±4% dry binder, based on fiber weight. This range wasequivalent to 26-31% binder on total fabric weight and provided afinished fabric weighing approximately 20 gms./sq.yd. The saturated webwas dried on a rotary drum dryer at 120° C. and then cured for 2 min. at150° C. in a forced air oven. Specimens were tested for wet strength(soaked 5 min. in a 0.5% Aerosol OT solution) and dry strength in thecross machine direction (CD).

    ______________________________________                                        Fabric Treatment       Strength                                                            %     Basis   (lbs./linear inch)                                 Latex          Pickup  Wt.     CD Wet CD Dry                                  ______________________________________                                        MEDHEU Polymer Latex                                                                         44      20.1    1.18   1.94                                    NMA Polymer Latex                                                                            40      20.8    1.27   1.83                                    (comparative)                                                                 ______________________________________                                    

The results show that the formaldehyde-free binder containing theself-crosslinking imidozolidinone-containing polymer provided anon-woven textile of comparable wet and dry strength to that preparedusing the prior art NMA-containing polymer that self-crosslinks with therelease of formaldehyde.

EXAMPLE X

This example describes the preparation of a latex polymer of 82% vinylacetate, 15% ethylene, and 5% of the EMDHEU monomer of Example IV.

A 1-liter stirred autoclave was charged with 213.5 g. distilled water,0.011 g. FeSO₄, 0.1% in water, 0.057 g. of a 75% solution of sodiumdioctyl sulfosuccinate, 1.44 g. of a 80% solution of sodium dihexylsulfosuccinate, 0.18 g. sodium acetate, and 2.28 g. acetic acid. Thereactor was purged and evacuated with nitrogen three times. Afterpurging, 35 g. vinyl acetate was loaded into the reactor. It waspressurized to 500 psi with ethylene and agitation was started.

A monomer pre-emulsion, designated S-1, was prepared by mixing with highspeed agitation 85 g. distilled water, 0.5 g. calcium acetate, 5.0 g.partially ethoxylated phosphoric acid, 5.0 g. ethoxylated nonylphenol(40 moles EO), 50.0 g. MPEDHEU monomer at 20% solids, and 245.0 g.vinylacetate.

Catalyst solutions, designated S-2 and S-3 respectively, were preparedby mixing 1.31 g. sodium persulfate and 17.5 g. distilled water and bymixing 0.52 g. sodium formaldehyde sulfoxylate and 17.5 g. distilledwater.

The reactor contents were heated to 40° C. under 500 psi ethylenepressure. At temperature, the monomer pre-emulsion S-1, the oxidant S-2and the reductant S-3 were added over a 6 hr. period. The reactiontemperature was allowed to rise to 70° C. and was maintained at thattemperature during the entire polymerization. At the end of theaddition, the pressure source was isolated and the reactor pressure wasallowed to drop over 2 hr. while maintaining the mixture at 70° C. Thereactor was then cooled and the resultant latex discharged.

The latex was 41.1% solids. Conversion was 99%. The latex had thefollowing properties: a pH of 4.2; intrinsic viscosity of 2.44 dl./g. inDMF; Brookfield viscosity of 25 cps.; particle size of 0.19 mm; and grit(200 mesh) of 20 ppm unfiltered. The Tg of the polymer was 30 3° C.

EXAMPLE XI

Using procedures outlined in Examples IX and X, latex polymers of 48.5%vinyl acetate, 48.5% butyl acrylate, and 3% of the indicatedimidazolidinones were prepared. All values are based on 100 parts of themajor monomer component and are expressed as active ingredient.

The initial charge was prepared by mixing 76.6 parts distilled water,0.155 parts of a 31% solution of disodium ethoxylated alcohol half esterof sulfosuccinic acid, 0.42 part of a 70% solution of ethoxylated octylphenol (30 mole EO), 10 parts vinyl acetate, 1 part butyl acrylate, 0.12part ammonium persulfate, and 0.04 parts sodium acetate.

The monomer pre-emulsion was prepared from 15.7 parts distilled water,40 parts vinyl acetate, 49 parts butyl acrylate, 3 parts of theimidazolidinone monomer described hereafter, 0.62 part disodiumethoxylated half ester of sulfosuccinic acid, and 0.7 part of a 70%solution of ethoxylated octyl phenol (30 mole EO). The catalyst used wasprepared from 8 parts distilled water and 0.16 part ammonium persulfate.

Latex A prepared using the EADHEU monomer of Example II had a solidscontent of 48.3%. Conversion was 98%. It had a pH of 3.9; intrinsicviscosity of 1.524 dl./g. in DMF; viscosity of 30 cps.; particle size of0.25 mm.; and grit (200 mesh) of 60 ppm. unfiltered. The % insolublesuncured (air-dried) and cured were 45 and 90%, respectively.

Latex B prepared using the EMDHEU monomer of Example IV had a solidscontent of 48.2%. Conversion was 98%. It had a pH of 4.2; intrinsicviscosity of 1.19 dl./g. in DMF; Brookfield viscosity of 77 cps.;particle size of 0.15 mm.; and grit (200 mesh) of 30 ppm. unfiltered.The % insolubles uncured and cured were 11 and 75%, respectively.

EXAMPLE XII

This example describes the preparation of a latex polymer of 87.4% ethylacrylate, 9.7% methyl methacrylate, and 2.9% of the ADHEU monomer ofEXAMPLE III--Part A. The polymerization procedure previously describedwas used.

The initial charge was prepared from 71.0 parts distilled water, 0.20part sodium dodecylbenzene sulfonate, 0.40 part of ethoxylated octylphenol (30 mole EO), 10 parts ethyl acrylate, and 0.15 part ammoniumpersulfate. The monomer pre-emulsion was prepared from 13.1 partsdistilled water, 80.0 parts ethyl acrylate, 10.0 parts methylmethacrylate, 0.6 part sodium dodecylbenzene sulfonate, and 1.55 partsof ethoxylated octyl phenol (30 mole EO). The self-crosslinkingfunctional monomer solution consisted of 3 parts of the ADHEU monomerand 12.2 parts water. The catalyst solution contained 10 parts water,0.2 part ammonium persulfate, and 0.1 part sodium bicarbonate.

The resulting latex had a solids content of 47.7%; a pH of 3.2;intrinsic viscosity of 0.603 dl./g. in DMF; Brookfield viscosity of 400cps.; particle size of 0.17 mm.; and grit (200 mesh) of 10 ppm. Theconversion was 95.8%.

EXAMPLE XIII

This example describes the prepration of a polyvinyl alcohol-stabilizedlatex polymer of about 97.1% vinyl acetate and 2.9% of the MEDHEUmonomer of Example I.

A 2-liter reactor was charged with an initial mixture of 288 partsdistilled water, 6 parts medium viscosity 88% polyvinyl alcohol, 9 partshigh viscosity 88% polyvinyl alcohol, 0.46 parts ammonium persulfate,and 50 parts vinyl acetate. The mixture was heated to reflux (about 72°C.). To the heated mixture were slowly added a pre-emulsion of 90.9parts distilled water, 0.2 parts medium viscosity 88% polyvinyl alcohol,75.0 parts of the MEDHEU monomer (20%), 0.45 parts hih viscosity 88%polyvinyl alcohol, and 45 parts vinyl acetate and a catalyst solution of26.5 parts distilled water, 0.75 parts 28% ammonium hydroxide solution,and 0.25 parts ammonium persulfate. The pre-emulsion and catalystsolution were added at a rate sufficient to maintain reflux (over about3 hr.). After the addition was completed, the batch was cooled anddischarged. The resulting latex had a solids content of 52.3%, a pH of4.6, and Brookfield viscosity of 7000 cps.

Now that the preferred embodiments of the invention have been describedin detail, various modifications and improvements thereon will becomereadily apparent to those skilled in the art. Accordingly, the spiritand scope of the present invention are to be limited only by theappended claims, and not by the foregoing specification.

What is claimed is:
 1. As a composition of matter, an imidazolidinone monomer having the structure: ##STR27## wherein R¹ is hydrogen or a linear or branched C₁ -C₆ alkyl group when attached to a nitrogen; X is a divalent radical selected from the group consisting of ##STR28## with R being hydrogen or a methyl group, m being an integer from 0-5, and n being an integer from 1-5; R₂ is hydrogen or a methyl group; R³ is hydrogen or a ##STR29## group, with R¹ being hydrogen or a linear or branched C₁ -C₆ alkyl or hydroxyalkyl when attached to an oxygen; and R₄ and R₅ are independently hydrogen or a C₁ -C₄ linear or branched alkyl group.
 2. The composition of claim 1, wherein R¹ is hydrogen or a C₁ -C₄ straight chain alkyl group.
 3. The composition of claim 1, wherein R² is hydrogen.
 4. The composition of claim 1, wherein X is ##STR30##
 5. The composition of claim 1, wherein R⁴ and R⁵ are hydrogen or methyl groups.
 6. The composition of claim 1, wherein R¹ is hydrogen or a C₁ -C₄ linear alkyl group; R² is hydrogen or a methyl group; X is --(CH₂)_(m--) with m being 0 or 1, ##STR31## and R⁴ and 4⁵ are hydrogen or methyl groups.
 7. The composition of claim 1, wherein R¹, R³, R⁴ and R⁵ are hydrogen, R² is a methyl group, and X is ##STR32## or wherein R¹ is an ethyl group, R², R³, R⁴ and R⁵ are hydrogen, and X is --CH₂ --; or wherein R¹, R², R³, R⁴ and R⁵ are hydrogen and X is --CH₂ --; or wherein R¹ and R² are methyl groups, R³, R⁴, and R⁵ are hydrogen, and X is ##STR33## or wherein R¹ is a n-butyl group, R² is a methyl group, R³, R⁴ and R⁵ are hydrogen, and X is --CH₂ --; or wherein R¹, R², R⁴ and R⁵ are hydrogen, R³ is ##STR34## and X is ##STR35## or wherein R¹, R³, R⁴ and R⁵ are hydrogen, R² is a methyl group, and X is ##STR36## or wherein R¹, R² R³, R⁴ and R⁵ are hydrogen and X is ##STR37##
 8. As a composition of matter, an imidazolidinone monomer having the structure: ##STR38## where R¹ is hydrogen or a linear or branched C₁ -C₆ alkyl group, X is a divalent radical selected from the group consisting of --(CH₂)_(m) --, ##STR39## with R being hydrogen or a methyl group, m being an integer from 0-5, and n being an integer from 1-5; R² is hydrogen or a methyl group; R³ is hydrogen; and R⁴ and R⁵ are independently hydrogen or a C₁ -C₄ linear or branched alkyl group.
 9. The composition of claim 8, wherein R¹ is hydrogen or a C₁ -C₄ straight chain alkyl group.
 10. The composition of claim 8, wherein R² is hydrogen.
 11. The composition of claim 8, wherein X is ##STR40##
 12. The composition of claim 8, wherein R⁴ and R⁵ are hydrogen or methyl groups.
 13. The composition of claim 8, wherein R¹ is hydrogen or a C₁ -C₄ linear alkyl group; R² is hydrogen or a methyl group; X is --(CH₂)_(m) -- with m being 0 or 1, ##STR41## or and R⁴ and R⁵ are hydrogen or methyl groups.
 14. The composition of claim 8, wherein R¹, R⁴ and R⁵ are hydrogen, R² is a methyl group, and X is ##STR42## or wherein R¹ is an ethyl group, R², R⁴ and R⁵ are hydrogen, and X is --CH₂ --; or wherein R¹, R², R⁴ and R⁵ are hydrogen and X is --CH₂ --; or wherein R¹ and R² are methyl groups, R⁴ and R⁵ are hydrogen, and X is ##STR43## or wherein R¹ is a n-butyl group, R² is a methyl group, R⁴ and R⁵ are hydrogen, and X is --CH₂ --; or wherein R¹, R⁴ and R⁵ are hydrogen, R² is a methyl group, and X is ##STR44## or wherein R¹, R², R⁴ and R⁵ are hydrogen and X is ##STR45##
 15. As a composition of matter, an imidazolidionone monomer having the structure: ##STR46## wherein R¹ is hydrogen or a linear or branched C₁ -C₆ alkyl group when attached to a nitrogen; X is a divalent radical selected from the group consisting of ##STR47## with R being hydrogen or a methyl group, m being an integer from 0-5, and n being an integer from 1-5; R² is a methyl group; R³ is hydrogen or a ##STR48## group, with R¹ being hydrogen or a linear or branched C₁ -C₆ alkyl or hydroxyalkyl when attached to an an oxygen; and R⁴ and R⁵ are independently hydrogen or a C₁ -C₄ linear or branched alkyl group.
 16. The composition of claim 15, wherein R¹ is hydrogen or a C₁ -C₄ straight chain alkyl group.
 17. The composition of claim 15, wherein X is ##STR49##
 18. The composition of claim 15, wherein R⁴ and R⁵ ar hydrogen or methyl groups.
 19. The composition of claim 15, wherein R¹ is hydrogen or a C₁ -C₄ linear alkyl group; X is --(CH₂)_(m--) with m being 0 or 1, ##STR50## and R⁴ and R⁵ are hydrogen or methyl groups.
 20. The composition of claim 15, wherein R¹, R³, R⁴ and R⁵ are hydrogen, and X is ##STR51## or wherein R¹ is a methyl group, R³, R⁴, and R⁵ are hydrogen, and X is ##STR52## or wherein R¹ is a n-butyl group, R³, R⁴ and R⁵ are hydrogen, and X is --CH₂₋₋ ;or wherein R¹, R³, R⁴ and R⁵ are hydrogen and X is ##STR53## 